Transparent bio-based polyamide resin composition and continuous fiber-reinforced transparent bio-based polyamide composite

Abstract

The application discloses a kind of transparent bio-based polyamide resin compositions and continuous fiber reinforced transparent bio-based polyamide composite materials.The transparent bio-based polyamide resin compositions include the following components by weight fraction: transparent bio-based polyamide resin 80-99 parts, antioxidant 0.2-1.2 parts, lubricant 0-1 part, compatible agent 0-15 parts and coupling agent 0-1 part.The continuous fiber reinforced transparent bio-based polyamide composite material includes transparent bio-based polyamide resin composition and fiber, wherein the fiber accounts for the mass percentage of the continuous fiber reinforced transparent bio-based polyamide composite material is 35%-75%.The continuous fiber reinforced transparent bio-based polyamide composite material of the application has high fiber content, good mechanical properties, and is recyclable, and can be applied to aerospace, military, automotive materials, sports equipment, building materials or electronic and electrical fields.

Description

Technical Field

[0001] This invention relates to a transparent bio-based polyamide resin composition, a continuous fiber reinforced transparent bio-based polyamide composite material, its preparation method, and its application. Background Technology

[0002] Compared to thermosetting materials, thermoplastic materials do not require cross-linking and curing, can be processed and molded multiple times, and have more convenient and efficient molding processes. Therefore, thermoplastic materials have maintained stable and continuous development in recent years, especially fiber-reinforced thermoplastic materials. The matrix resin of fiber-reinforced thermoplastic materials can be made of thermoplastic materials such as polypropylene, polyamide, and polyester, and the fibers can be made of glass fiber, carbon fiber, aramid fiber, etc., among which glass fiber is the most commonly used.

[0003] Fiber-reinforced thermoplastic materials are mainly classified into short-fiber (2-4mm) reinforced thermoplastic materials, long-fiber (12-24mm) reinforced thermoplastic materials, fiber mat reinforced thermoplastic materials, continuous fiber reinforced thermoplastic materials, and thermoplastic composite core boards. Among these, short-fiber reinforced thermoplastic materials, due to their relatively poor strength, cannot meet the performance requirements of structural materials, leading to the development of long-fiber reinforced thermoplastic materials. Continuous fibers offer better reinforcement than both short and long fibers, significantly improving mechanical properties and fatigue resistance, thus attracting active research in recent years. Initially, continuous fiber reinforced thermoplastic materials focused primarily on aerospace and military applications, but since 2003, they have gradually been applied to automotive materials, sporting goods, and construction industries. With the development of the automotive and electronics industries, the demand for continuous fiber reinforced thermoplastic materials will continue to grow, making the research and promotion of continuous fiber reinforced thermoplastic materials of great significance.

[0004] Continuous fiber reinforced thermoplastics (CFRPs) offer long-term preservation, excellent overall performance, wide moldability, high production efficiency, and the ability to be repeatedly processed and recycled. Therefore, research on CFRPs has been very active since their development in the early 1970s. Domestic research on CFRPs also began in the late 1980s. The main production processes for CFRPs include melt processing, solution processing, powder processing, and calendering. However, these methods require expensive molding equipment, and the resin cannot effectively impregnate and disperse the fibers during molding, resulting in low fiber content and poor mechanical properties in CFRP composites, thus limiting the application of matrix resins in CFRPs. Summary of the Invention

[0005] To address the shortcomings of existing continuous fiber reinforced composite materials, such as low fiber content, poor mechanical properties, and high cost, this invention provides a transparent bio-based polyamide resin composition, a continuous fiber reinforced transparent bio-based polyamide composite material, its preparation method, and its applications. The transparent bio-based polyamide resin composition of this invention exhibits good fiber wettability; the continuous fiber reinforced composite material prepared based on this transparent bio-based polyamide resin composition has high fiber content, good mechanical properties, and is recyclable.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] One of the technical solutions is a transparent bio-based polyamide resin composition comprising the following components in parts by weight: 80-99 parts of transparent bio-based polyamide resin, 0.2-1.2 parts of antioxidant, 0-1 part of lubricant, 0-15 parts of compatibilizer, and 0-1 part of coupling agent.

[0008] In one embodiment of the present invention, the relative viscosity of the transparent bio-based polyamide resin is 1.5 to 3.5, and more preferably 2.3 to 2.7; the water content is ≤5000ppm, and more preferably ≤1500ppm.

[0009] In one embodiment of the present invention, the bio-based content of the transparent bio-based polyamide resin is 21-41%, for example 31%.

[0010] In one embodiment of the present invention, the glass transition temperature of the transparent bio-based polyamide resin is 130-170°C, preferably 140-160°C.

[0011] In one embodiment of the present invention, the heat distortion temperature (1.8 MPa) of the transparent bio-based polyamide resin is 130-160°C, preferably 145-155°C.

[0012] In one embodiment of the present invention, the transparent bio-based polyamide resin comprises more than 90%, preferably 90-98%; and the haze is less than 3.0%, more preferably 1.6-2.0%.

[0013] In one embodiment of the present invention, the transparent bio-based polyamide resin has a tensile strength of 80 MPa or higher, more preferably 80-95 MPa; a tensile modulus of 2000 MPa or higher, more preferably 2000-2400 MPa; a flexural strength of 100 MPa or higher, more preferably 100-130 MPa; a flexural modulus of 2500 MPa or higher, more preferably 2500-3500 MPa; and a notched impact strength of 10 KJ / m. 2 The above, and more preferably 10–13 KJ / m 2 .

[0014] In some specific implementations, the transparent bio-based polyamide resin is commercially available transparent polyamide E-5000, purchased from Kaisai (Jinxiang) Biomaterials Co., Ltd.

[0015] In this invention, the raw material monomer pentanediamine used in the transparent bio-based polyamide resin is prepared through bio-fermentation.

[0016] In this invention, the content of the transparent bio-based polyamide resin is preferably 90-95 parts, for example 94.5, 93.5, 92.5 or 94.0 parts.

[0017] In this invention, the antioxidant is selected from one or more of hindered phenolic antioxidants, hindered amine antioxidants, and phosphite antioxidants; preferably, it is a combination of hindered amine antioxidants and phosphite antioxidants. The hindered phenolic antioxidant can be conventional in the art, such as antioxidant 1010. The hindered amine antioxidant can be conventional in the art, such as antioxidant 1098 (CAS 23128-74-7). The phosphite antioxidant can be conventional in the art, such as antioxidant 168 (CAS 31570-04-4) and antioxidant S9228.

[0018] Preferably, the antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010, and antioxidant S9228. More preferably, the antioxidant is a combination of antioxidant 168 and antioxidant 1098; wherein the mass ratio of antioxidant 168 to antioxidant 1098 is preferably 1:1.

[0019] In this invention, the content of the antioxidant is preferably 0.4-0.8 parts, for example 0.4, 0.5, 0.6 or 0.8 parts.

[0020] In this invention, the lubricant may include an external lubricant and an internal lubricant; wherein, the mass ratio of the external lubricant to the internal lubricant is preferably 1:1.

[0021] The external lubricant can be conventional in the art, such as WAXC purchased from Clariant GmbH, Germany. The internal lubricant can be conventional in the art, such as WAXE purchased from Clariant GmbH, Germany.

[0022] In this invention, the content of the lubricant is preferably 0.1-0.8 parts, for example 0.3, 0.4, 0.5 or 0.6 parts.

[0023] In this invention, the compatibilizer may be selected from one or more of polyolefin-grafted maleic anhydride compatibilizers and rubber elastomer-grafted maleic anhydride compatibilizers. The polyolefin-grafted maleic anhydride compatibilizer may be conventional in the art, such as PP-g-MAH or POE-g-MAH. The rubber elastomer-grafted maleic anhydride compatibilizer may be conventional in the art, such as EPDM-g-MAH.

[0024] In this invention, the content of the compatibilizer is preferably 3-15 parts, more preferably 6-8 parts, for example 4, 5, 6, 8, 10 or 12 parts.

[0025] In this invention, the coupling agent may be selected from one or more of silane coupling agents, carbonate coupling agents, and aluminate coupling agents; preferably, it is a silane coupling agent, such as coupling agent KH550, coupling agent KH560, or coupling agent KH570. The coupling agent is generally selected according to the composition and surface structure of the fiber used.

[0026] In this invention, the amount of the coupling agent is preferably 0.1-0.8 parts, for example 0.2, 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 parts.

[0027] In some preferred embodiments, the transparent bio-based polyamide resin composition comprises the following components in parts by weight: 90-95 parts transparent bio-based polyamide resin, 0.4-0.8 parts antioxidant, 0.1-0.8 parts lubricant, 3-15 parts compatibilizer, and 0.1-0.8 parts coupling agent.

[0028] In a preferred embodiment, the transparent bio-based polyamide resin composition comprises the following components in parts by weight: 92-94 parts transparent bio-based polyamide resin, 0.2-0.4 parts antioxidant 1098, 0.2-0.4 parts antioxidant 168, 0.2-0.3 parts internal lubricant WAXE, 0.2-0.3 parts external lubricant WAXC, 6-8 parts compatibilizer, and 0.2-0.6 parts silane coupling agent.

[0029] In this invention, the transparent bio-based polyamide resin composition can be prepared using conventional methods in the art, generally by mixing the components evenly. The mixing can be performed using conventional mixing equipment in the art, such as a high-speed mixer.

[0030] Technical Solution Two: A continuous fiber reinforced transparent bio-based polyamide composite material, comprising the transparent bio-based polyamide resin composition and fiber as described above, wherein the fiber accounts for 35%-75% of the mass percentage of the continuous fiber reinforced transparent bio-based polyamide composite material.

[0031] In this invention, the fiber accounts for 50-70% of the mass percentage of the continuous fiber-reinforced transparent bio-based polyamide composite material, for example, 60%, 65% or 70%.

[0032] In this invention, the type of fiber can be conventional in the art, such as carbon fiber, glass fiber, basalt fiber, or aramid fiber. The fiber is preferably a continuous long fiber, and more preferably, it is a continuous long glass fiber. The diameter of the single filament of the continuous long glass fiber can be 8-15 μm, preferably 8-10 μm. The linear density of the continuous long glass fiber is 1000-3600 Tex, preferably 1200 Tex or 2400 Tex. For example, the continuous long glass fiber is 1200 Tex continuous long glass fiber purchased from Owens Corning (OC) or 2400 Tex continuous long glass fiber purchased from Jushi.

[0033] Preferably, the fiber is a continuous long carbon fiber; the continuous long carbon fiber is preferably a polyacrylonitrile carbon fiber; the number of monofilaments of the continuous long carbon fiber can be 20,000-30,000, preferably 12,000 (12K) or 24,000 (24K); the diameter of the monofilaments of the continuous long carbon fiber can be 5-10 μm, preferably 6-8 μm. For example, the continuous long carbon fiber is Toray T700 with a specification of 24K, or Guangwei Composites continuous long carbon fiber 700S with a specification of 12K or 24K.

[0034] In this invention, preferably, the continuous fiber reinforced transparent bio-based polyamide composite material is in the form of a unidirectional prepreg tape. The unidirectional prepreg tape refers to a strip-shaped prepreg made by impregnating mutually parallel continuous fibers with resin.

[0035] In this invention, preferably, the thickness of the continuous fiber reinforced transparent bio-based polyamide composite material is 0.15-0.5 mm.

[0036] In this invention, when the fiber is a continuous long glass fiber, the tensile strength of the continuous fiber reinforced transparent bio-based polyamide composite material is 500-1500 MPa, more specifically 800-1500 MPa; the tensile modulus is 20-60 GPa, more specifically 30-60 GPa; and the elongation at break is 1.5-4.0%, more specifically 2.8-4.0%.

[0037] In this invention, when the fiber is a continuous long carbon fiber, the tensile strength of the continuous fiber reinforced transparent bio-based polyamide composite material is 1300-2000 MPa; the tensile modulus is 80-140 GPa; and the elongation at break is 1.5-4.0%, more specifically 2.5-4.0%.

[0038] Technical Solution Three: A method for preparing a continuous fiber-reinforced transparent bio-based polyamide composite material as described above, comprising the following steps:

[0039] S1. Prepare a slurry containing a transparent bio-based polyamide resin composition powder;

[0040] S2. The fiber is drawn through the mud to allow the transparent bio-based polyamide resin composition powder to be impregnated and dispersed into the fiber. It is heated to ensure full impregnation, and then extruded through a pultrusion die to obtain the final product.

[0041] In this process, the proportion of transparent bio-based polyamide resin composition powder in the slurry and the traction speed are adjusted to control the mass percentage of the fiber in the continuous fiber reinforced polyamide composite material to be 35%-75%.

[0042] In step S1 of the present invention, the mud containing transparent bio-based polyamide resin composition powder comprises, by mass percentage: transparent bio-based polyamide resin composition powder: 10-50%, water: 50-90%, water-soluble polymer: 0.1-5%, surfactant: 0.1-5%, and viscosity reducer: 0.1-5%.

[0043] In one embodiment, the density of the transparent bio-based polyamide resin composition powder is 1.0-1.5.

[0044] In one embodiment, the particle size D50 of the transparent bio-based polyamide resin composition powder is less than 50 micrometers, preferably less than or equal to 5 micrometers. The smaller the particle size, the easier it is to impregnate into the fibers.

[0045] In one embodiment, the water-soluble polymer is selected from one or more of nonionic water-soluble cellulose, nonionic water-soluble hydroxypropyl methylcellulose, and polyvinyl alcohol.

[0046] In one embodiment, the surfactant is selected from one or more of Fluorad 431, octadecylbenzyldimethylammonium chloride, and castor oil polyoxyethylene ether.

[0047] In one embodiment, the viscosity reducer is selected from one or more of the 1,3-butanediol and ethylene glycol series.

[0048] In one embodiment, the viscosity of the mud is 0.1-100 cps, preferably 2-30 cps.

[0049] In this invention, the method for preparing the slurry containing the transparent bio-based polyamide resin composition powder includes: taking materials according to the proportions of each component in the above-mentioned slurry; first, mixing and stirring an appropriate amount of water, surfactant, and viscosity reducer to obtain a solution; dissolving the water-soluble polymer separately with water (water at 40-100℃), and then adding it to the above solution while stirring; slowly adding the transparent bio-based polyamide resin composition powder in batches to the above solution while stirring, thus obtaining the slurry. In this invention, there is no particular limitation on the ratio of water used in the two steps, as long as it can achieve a dissolving effect; those skilled in the art can choose according to actual needs. In this invention, the stirring speed is 500-1000 r / min.

[0050] In this invention, preferably, the fiber accounts for 50-70% of the mass percentage of the continuous fiber-reinforced transparent bio-based polyamide composite material, for example, 60% or 65%.

[0051] In step S2, before the fibers are drawn through the mud, the fibers undergo the following process: the fibers are unwound from the yarn rack by a tension controller, pass through a yarn separating frame, and enter a yarn spreading system to fully spread each filament bundle. Then, they are drawn through the mud, thereby ensuring that the transparent bio-based polyamide resin composition powder is uniformly impregnated and dispersed into the fiber bundles. In step S2, the fibers are as described above.

[0052] In step S2, the traction is performed using a traction device, and the traction speed can be 3-12 m / min, for example 6 m / min.

[0053] In step S2, the heating temperature is 290-310℃. This invention uses heating to both dehydrate the impregnated fibers and melt the resin.

[0054] In this invention, the continuous fiber reinforced transparent bio-based polyamide composite material prepared by the method of preparing the continuous fiber reinforced transparent bio-based polyamide composite material is preferably in the form of a unidirectional prepreg tape.

[0055] In this invention, preferably, the thickness of the continuous fiber reinforced transparent bio-based polyamide composite material prepared by the method of preparing the continuous fiber reinforced transparent bio-based polyamide composite material is 0.15-0.5 mm.

[0056] Technical Solution Four: A molded article comprising a continuous fiber-reinforced transparent bio-based polyamide composite material as described above.

[0057] Technical Solution 5: The application of a continuous fiber reinforced transparent bio-based polyamide composite material as described above in the aerospace, military, automotive, sports equipment, building materials or electronic and electrical appliances fields.

[0058] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0059] The reagents and raw materials used in this invention are all commercially available.

[0060] The positive and progressive effects of this invention are as follows:

[0061] 1. This invention uses transparent bio-based polyamide resin as raw material:

[0062] (1) The monomer pentanediamine in the raw material is prepared by bio-fermentation, and the bio-based content is between 21% and 41%, which is in line with the concept of sustainable development of material sources;

[0063] (2) The transparent bio-based polyamide resin composition prepared using the transparent bio-based polyamide described in this invention has good wettability to fibers;

[0064] (3) The production process does not require twin-screw extruders and resin melt extrusion impregnation rollers, etc., which reduces equipment investment and lowers costs.

[0065] 2. The continuous fiber-reinforced transparent bio-based polyamide composite material of the present invention:

[0066] (1) High fiber content, ranging from 35% to 75%;

[0067] (2) It has excellent mechanical properties;

[0068] (3) The fibers are evenly distributed, with no exposed fibers, and are easy to process;

[0069] (4) The thickness of the composite material can be set between 0.15-0.5mm as needed, which can provide more design freedom for the product;

[0070] (5) The final molded product containing the continuous fiber reinforced transparent bio-based polyamide composite material described in this invention is recyclable and reusable, with high resource utilization.

[0071] 3. The preparation method of the continuous fiber-reinforced transparent bio-based polyamide composite material of the present invention is simple and feasible. Water is used as the dispersion medium. Water has a relatively low boiling point and is easy to remove from the slurry. It is also widely available and does not pollute the environment. In addition, the fiber content can be adjusted by adjusting the proportion of transparent bio-based polyamide resin in the slurry or the thickness of the unidirectional strip, making it more convenient to adjust the fiber content. Detailed Implementation

[0072] The present invention is further illustrated below by way of examples, but these examples do not limit the invention to the scope of the embodiments described. Experimental methods in the following examples, unless otherwise specified, were performed according to conventional methods and conditions, or as selected in the product instructions. The sources of the raw materials in the following examples and comparative examples are explained below:

[0073] Transparent bio-based polyamide resin E-5000: relative viscosity 2.35; water content 900ppm; bio-based content 31%; glass transition temperature 150℃; heat distortion temperature (1.8MPa) 145℃; light transmittance 90.2%, haze 1.91%; tensile strength 90MPa, tensile modulus 2300MPa, flexural strength 110MPa, flexural modulus 2600MPa, notched impact strength 11KJ / m 2 Purchased from Kaisai (Jinxiang) Biomaterials Co., Ltd.;

[0074] Antioxidants were purchased from BASF Group, Germany; WAXE and WAXC were purchased from Clariant AG, Germany; compatibilizers were purchased from Shanghai Jiayirong Polymer Co., Ltd.; coupling agents were purchased from Hangzhou Jessica Chemical Co., Ltd.; continuous long glass fibers were purchased from Owens Corning (OC), with a specification of 1200Tex; and continuous long carbon fibers were Toray T700, with a specification of 24K.

[0075] Example 1

[0076] 1. Preparation of transparent bio-based polyamide resin composition

[0077] The transparent bio-based resin composition used in this embodiment comprises the following components in parts by weight:

[0078] The following components were mixed: transparent bio-based polyamide resin E-5000 (94.5 parts), antioxidant 1098 (0.2 parts), antioxidant 168 (0.2 parts), internal lubricant WAXE (0.3 parts), external lubricant WAXC (0.3 parts), compatibilizer POE-g-MAH (4 parts), and coupling agent KH550 (0.5 parts). The above components were added to a high-speed mixer and mixed to obtain the transparent bio-based polyamide resin composition.

[0079] 2. Preparation of continuous fiber reinforced polyamide composites

[0080] S1. Prepare a slurry containing a transparent bio-based polyamide resin composition powder; wherein the slurry, by mass percentage, comprises: transparent bio-based polyamide resin composition powder (density 1.12, D50 = 10 micrometers): 10%, water: 88%, nonionic water-soluble hydroxypropyl methylcellulose: 0.5%, castor oil polyoxyethylene ether: 0.5%, 1,3-butanediol: 1.0%.

[0081] The specific preparation method is as follows: Take the materials according to the proportions of each component in the above mud. First, mix an appropriate amount of water, castor oil polyoxyethylene ether, and 1,3-butanediol at a high speed of 800 r / min to obtain a solution. Dissolve non-ionic water-soluble hydroxypropyl methylcellulose separately in deionized water at 80℃, and then add it to the above solution and stir for at least half an hour. Slowly add the transparent bio-based polyamide resin composition powder in batches to the above solution and stir at high speed for at least 6 hours. The viscosity of the resulting mud is 15 cps.

[0082] S2. Continuous long glass fibers are unwound from the yarn rack by a tension controller, passed through a yarn separating frame, and entered into a yarn spreading system to fully spread each filament bundle. Then, they are passed through a slurry by a traction device to allow transparent bio-based polyamide ultrafine powder to be evenly impregnated and dispersed into the fiber bundle. The traction speed is 6m / min. The fibers are heated to fully impregnate them at a temperature of 300℃. Finally, they are extruded through a pultrusion die to obtain the final product.

[0083] During the preparation process, the weight ratio of continuous long glass fiber to transparent bio-based polyamide resin composition powder in the slurry and the traction speed were adjusted to ensure a ratio of 65:35. The continuous long glass fiber reinforced polyamide composite material prepared above is a unidirectional prepreg tape, and its performance parameters are shown in Table 1.

[0084] Example 2

[0085] 1. Preparation of transparent bio-based polyamide resin composition

[0086] The transparent bio-based resin composition used in this embodiment comprises the following components in parts by weight:

[0087] The following components were mixed: transparent bio-based polyamide resin E-5000 (93.5 parts), antioxidant 1098 (0.3 parts), antioxidant 168 (0.3 parts), internal lubricant WAXE (0.2 parts), external lubricant WAXC (0.2 parts), compatibilizer POE-g-MAH (5 parts), and coupling agent KH550 (0.5 parts). The above components were added to a high-speed mixer and mixed to obtain the transparent bio-based polyamide resin composition.

[0088] 2. Preparation of continuous fiber reinforced polyamide composites

[0089] S1. Prepare a slurry containing a transparent bio-based polyamide resin composition powder; wherein the slurry, by mass percentage, comprises: transparent bio-based polyamide resin composition powder (density 1.15, D50 = 10 micrometers): 10%, water: 87%, nonionic water-soluble hydroxypropyl methylcellulose: 1.0%, castor oil polyoxyethylene ether: 1.0%, 1,3-butanediol: 1.0%.

[0090] The specific preparation method is as follows: Take the materials according to the proportions of each component in the above mud. First, mix an appropriate amount of water, castor oil polyoxyethylene ether, and 1,3-butanediol at a high speed of 800 r / min to obtain a solution. Dissolve non-ionic water-soluble hydroxypropyl methylcellulose separately in deionized water at 80°C, and then add it to the above solution and stir for at least half an hour. Slowly add the transparent bio-based polyamide resin composition powder in batches to the above solution and stir at high speed for at least 6 hours. The viscosity of the resulting mud is 18 cps.

[0091] S2. Continuous long glass fibers are unwound from the yarn rack by a tension controller, passed through a yarn separating frame, and entered into a yarn spreading system to fully spread each filament bundle. Then, they are passed through a slurry by a traction device to allow transparent bio-based polyamide ultrafine powder to be evenly impregnated and dispersed into the fiber bundle. The traction speed is 6m / min. The fibers are heated to fully impregnate them at a temperature of 300℃. Finally, they are extruded through a pultrusion die to obtain the final product.

[0092] During the preparation process, the weight ratio of continuous long glass fiber to transparent bio-based polyamide resin composition powder in the slurry and the traction speed were adjusted to ensure a ratio of 60:40. The continuous long glass fiber reinforced polyamide composite material prepared above is a unidirectional prepreg tape, and its performance parameters are shown in Table 1.

[0093] Example 3

[0094] 1. Preparation of transparent bio-based polyamide resin composition

[0095] The transparent bio-based resin composition used in this embodiment comprises the following components in parts by weight:

[0096] The following components were added to a high-speed mixer: transparent bio-based polyamide resin E-5000: 94.0 parts; antioxidant 1098: 0.3 parts; antioxidant 168: 0.3 parts; internal lubricant WAXE: 0.3 parts; external lubricant WAXC: 0.3 parts; compatibilizer POE-g-MAH: 4 parts; coupling agent KH550: 0.8 parts. The above components were mixed to obtain the transparent bio-based polyamide resin composition.

[0097] 2. Preparation of continuous fiber reinforced polyamide composites

[0098] S1. Prepare a slurry containing a transparent bio-based polyamide resin composition powder; wherein the slurry, by weight percentage, comprises: transparent bio-based polyamide resin composition powder (density 1.2, D50 = 10 micrometers): 12%, water: 86%, nonionic water-soluble hydroxypropyl methylcellulose: 0.5%, castor oil polyoxyethylene ether: 0.5%, 1,3-butanediol: 1.0%.

[0099] The specific preparation method is as follows: Take the materials according to the proportions of each component in the above mud. First, mix an appropriate amount of water, castor oil polyoxyethylene ether, and 1,3-butanediol at a high speed of 800 r / min to obtain a solution. Dissolve non-ionic water-soluble hydroxypropyl methylcellulose separately in deionized water at 80℃, and then add it to the above solution and stir for at least half an hour. Slowly add the transparent bio-based polyamide resin composition powder in batches to the above solution and stir at high speed for at least 6 hours. The viscosity of the resulting mud is 26 cps.

[0100] S2. Continuous long glass fibers are unwound from the yarn rack by a tension controller, pass through a yarn separating frame, and enter the yarn spreading system to fully spread each filament bundle. Then, they are passed through a slurry by a traction device to allow transparent bio-based polyamide ultrafine powder to be evenly impregnated and dispersed into the fiber bundle. The traction speed is 7m / min. The fiber bundle is heated to ensure full impregnation at a temperature of 300℃. Finally, it is extruded through a pultrusion die to obtain the final product.

[0101] During the preparation process, the weight ratio of continuous long glass fiber to transparent bio-based polyamide resin composition powder in the slurry and the traction speed were adjusted to ensure a ratio of 70:30. The continuous long glass fiber reinforced polyamide composite material prepared above is a unidirectional prepreg tape, and its performance parameters are shown in Table 1.

[0102] Example 4

[0103] 1. Preparation of transparent bio-based polyamide resin composition

[0104] The transparent bio-based resin composition used in this embodiment comprises the following components in parts by weight:

[0105] The following components were mixed: transparent bio-based polyamide resin E-5000 (92.5 parts), antioxidant 1098 (0.2 parts), antioxidant 168 (0.2 parts), internal lubricant WAXE (0.2 parts), external lubricant WAXC (0.2 parts), compatibilizer POE-g-MAH (6 parts), and coupling agent KH550 (0.7 parts). The above components were added to a high-speed mixer and mixed to obtain the transparent bio-based polyamide resin composition.

[0106] 2. Preparation of continuous fiber reinforced polyamide composites

[0107] S1. Prepare a slurry containing a transparent bio-based polyamide resin composition powder; wherein the slurry, by mass percentage, comprises: transparent bio-based polyamide resin composition powder (density 1.12, D50 = 5 micrometers): 10%, water: 88%, nonionic water-soluble hydroxypropyl methylcellulose: 0.6%, castor oil polyoxyethylene ether: 0.6%, 1,3-butanediol: 0.8%.

[0108] The specific preparation method is as follows: Take the materials according to the proportions of each component in the above mud. First, mix an appropriate amount of water, castor oil polyoxyethylene ether, and 1,3-butanediol at a high speed of 800 r / min to obtain a solution. Dissolve non-ionic water-soluble hydroxypropyl methylcellulose separately in deionized water at 80°C, and then add it to the above solution and stir for at least half an hour. Slowly add the transparent bio-based polyamide resin composition powder in batches to the above solution and stir at high speed for at least 6 hours. The viscosity of the resulting mud is 23 cps.

[0109] S2. Continuous long glass fibers are unwound from the yarn rack by a tension controller, passed through a yarn separating frame, and entered into a yarn spreading system to fully spread each filament bundle. Then, they are passed through a slurry by a traction device to allow transparent bio-based polyamide ultrafine powder to be evenly impregnated and dispersed into the fiber bundle. The traction speed is 6m / min. The fibers are heated to fully impregnate them at a temperature of 300℃. Finally, they are extruded through a pultrusion die to obtain the final product.

[0110] During the preparation process, the weight ratio of continuous long glass fiber to transparent bio-based polyamide resin composition powder in the slurry and the traction speed were adjusted to ensure that the weight ratio of continuous long glass fiber to transparent bio-based polyamide resin composition was 68:32. The continuous long glass fiber reinforced polyamide composite material prepared above is a unidirectional prepreg tape, and its performance parameters are shown in Table 1.

[0111] Example 5

[0112] The same method as in Example 1 was used, except that continuous long carbon fibers were used when preparing the continuous fiber reinforced polyamide composite.

[0113] Example 6

[0114] The same method as in Example 2 was used, except that continuous long carbon fibers were used when preparing the continuous fiber reinforced polyamide composite.

[0115] Example 7

[0116] The same method as in Example 3 was used, except that continuous long carbon fibers were used when preparing the continuous fiber reinforced polyamide composite material.

[0117] Example 8

[0118] The same method as in Example 4 was used, except that continuous long carbon fibers were used when preparing the continuous fiber reinforced polyamide composite material.

[0119] Comparative Example 1

[0120] The same method as in Example 1 was followed, except that commercially available EMS TR90 transparent polyamide was used when preparing the transparent polyamide resin composition.

[0121] Comparative Example 2

[0122] The same method as in Example 5 was followed, except that commercially available EMS TR90 transparent polyamide was used when preparing the transparent polyamide resin composition.

[0123] Comparative Example 3

[0124] The same method as in Example 1 was followed, except that commercially available Akema G850 transparent polyamide was used when preparing the transparent bio-based polyamide resin composition.

[0125] Comparative Example 4

[0126] The same method as in Example 5 was followed, except that commercially available Akema G850 transparent polyamide was used when preparing the transparent bio-based polyamide resin composition.

[0127] The continuous fiber reinforced polyamide composite unidirectional prepreg tapes of Examples 1-8 and Comparative Examples 1-4 were tested for performance according to the following test methods: (1) Fiber content: ASTM D5630; (2) Tensile strength: ASTM D3039; (3) Tensile modulus: ASTM D3039; (4) Elongation at break: ASTM D3039. The results are shown in Table 1.

[0128] Table 1

[0129]

[0130] As shown in Table 1, Examples 1-4 are transparent bio-based polyamide composites containing continuous long glass fibers. All have tensile strengths above 800 MPa, tensile moduli above 30 GPa, and elongation at break above 2.8%. Examples 5-8 are transparent bio-based polyamide composites containing continuous long carbon fibers. All have tensile strengths above 1300 MPa, tensile moduli above 80 GPa, and elongation at break between 1.5% and 4.0%. Comparative Examples 1 and 2 are commercially available EMS TR90 transparent polyamide composites containing continuous long glass fibers and continuous long carbon fibers, respectively. Their mechanical properties are inferior to those of the corresponding examples with similar fiber content. Similarly, Comparative Examples 3 and 4 are commercially available Akema G850 transparent polyamide composites containing continuous long glass fibers and continuous long carbon fibers, respectively. Their mechanical properties are also inferior to those of the corresponding examples with similar fiber content. In summary, the embodiments of the present invention exhibit excellent mechanical properties, and the transparent bio-based polyamides of the present invention all use bio-based pentamethylenediamine, which has a high carbon content, effectively reducing the use of fossil raw materials and thus reducing carbon emissions.

Claims

1. A continuous fiber-reinforced transparent bio-based polyamide composite material, characterized in that, The composite material comprises a transparent bio-based polyamide resin composition and fibers; the transparent bio-based polyamide resin composition comprises the following components in parts by weight: 80-99 parts of transparent bio-based polyamide resin, 0.2-1.2 parts of antioxidant, 0-1 part of lubricant, 0-15 parts of compatibilizer, and 0-1 part of coupling agent; the fibers account for 35%-75% of the mass percentage of the continuous fiber reinforced transparent bio-based polyamide composite material. The transparent bio-based polyamide resin has the following characteristics: a relative viscosity of 2.3–2.7, a glass transition temperature of 140–160℃, a heat distortion temperature of 145–155℃ under a test pressure of 1.8 MPa, a light transmittance of 90–98%, a haze of 1.6–2.0%, a tensile strength of 90–95 MPa, a tensile modulus of 2300–2400 MPa, a flexural strength of 110–130 MPa, a flexural modulus of 2500–2600 MPa, and a notched impact strength of 11–13 KJ / m. 2 .

2. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 1, characterized in that, The transparent bio-based polyamide resin has a water content ≤5000ppm; and / or, The transparent bio-based polyamide resin has a bio-based content of 21-41%; and / or, The content of the transparent bio-based polyamide resin is 90-95 parts.

3. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 1, characterized in that, The transparent bio-based polyamide resin has a water content of ≤1500ppm.

4. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 1, characterized in that, The antioxidant is selected from one or more of hindered phenolic antioxidants, hindered amine antioxidants, and phosphite antioxidants; And / or, the content of the antioxidant is 0.4 to 0.8 parts; And / or, the lubricant includes an external lubricant and an internal lubricant; And / or, the content of the lubricant is 0.1 to 0.8 parts; And / or, the compatibilizer is selected from one or more of polyolefin-grafted maleic anhydride compatibilizers and rubber elastomer-grafted maleic anhydride compatibilizers; And / or, the content of the compatibilizer is 3 to 15 parts; And / or, the coupling agent is selected from one or more of silane coupling agents, carbonate coupling agents, and aluminate coupling agents; And / or, the amount of the coupling agent used is 0.1 to 0.8 parts.

5. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 4, characterized in that, The antioxidant is a combination of hindered amine antioxidants and phosphite antioxidants; And / or, the mass ratio of the external lubricant to the internal lubricant is 1:1; And / or, the polyolefin grafted maleic anhydride compatibilizer is PP-g-MAH or POE-g-MAH; And / or, the rubber elastomer grafted with maleic anhydride compatibilizer is EPDM-g-MAH.

6. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 4, characterized in that, The antioxidant is selected from one or more of antioxidant 168, antioxidant 1098, antioxidant 1010 and antioxidant S9228; And / or, the external lubricant is WAXC, and the internal lubricant is WAXE; The coupling agent is a silane-based coupling agent.

7. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 4, characterized in that, The antioxidant is a combination of antioxidant 168 and antioxidant 1098; And / or, the content of the compatibilizer is 6 to 8 parts; And / or, the coupling agent is coupling agent KH550, coupling agent KH560 or coupling agent KH570.

8. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 7, characterized in that, The mass ratio of antioxidant 168 to antioxidant 1098 is 1:

1.

9. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 1, characterized in that, The fiber accounts for 50-70% of the mass percentage of the continuous fiber-reinforced transparent bio-based polyamide composite material. And / or, the type of fiber is carbon fiber, glass fiber, basalt fiber or aramid fiber; And / or, the fiber is a continuous long fiber; And / or, the continuous fiber reinforced transparent bio-based polyamide composite material is in the form of a unidirectional prepreg tape; And / or, the thickness of the continuous fiber reinforced transparent bio-based polyamide composite material is 0.15 to 0.5 mm.

10. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 9, characterized in that, The fiber is a continuous long glass fiber; the diameter of the single filament of the continuous long glass fiber is 8-15 μm; the linear density of the continuous long glass fiber is 1000-3600 TeX.

11. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 9, characterized in that, The fiber is a continuous long glass fiber, and the tensile strength of the continuous fiber reinforced transparent bio-based polyamide composite material is 500-1500 MPa; the tensile modulus is 20-60 GPa; and the elongation at break is 1.5-4.0%.

12. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 9, characterized in that, The fiber is a continuous long carbon fiber.

13. The continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 12, characterized in that, The continuous long carbon fiber is a polyacrylonitrile carbon fiber; And / or, the number of monofilaments of the continuous long carbon fiber is 20,000 to 30,000; And / or, the diameter of the single filament of the continuous long carbon fiber is 5 to 10 μm; And / or, the tensile strength of the continuous fiber reinforced transparent bio-based polyamide composite material is 1300-2000 MPa; the tensile modulus is 80-140 GPa; and the elongation at break is 1.5-4.0%.

14. A method for preparing a continuous fiber-reinforced transparent bio-based polyamide composite material as described in any one of claims 1 to 13, comprising the following steps: S1. Prepare a slurry containing a transparent bio-based polyamide resin composition powder; S2. The fiber is drawn through the mud to allow the transparent bio-based polyamide resin composition powder to be impregnated and dispersed into the fiber. It is heated to ensure full impregnation, and then extruded through a pultrusion die to obtain the final product. In this process, by adjusting the proportion of transparent bio-based polyamide resin composition powder in the mud and the traction speed, the mass percentage of the fiber in the continuous fiber reinforced polyamide composite material is controlled to be 35% to 75%.

15. The method for preparing the continuous fiber reinforced transparent bio-based polyamide composite material according to claim 14, characterized in that, In step S1, the slurry containing the transparent bio-based polyamide resin composition powder comprises, by weight percentage: transparent bio-based polyamide resin composition powder: 10-50%, water: 50-90%, water-soluble polymer: 0.1-5%, surfactant: 0.1-5%, and viscosity reducer: 0.1-5%; Wherein, the density of the transparent bio-based polyamide resin composition powder is 1.0 to 1.5; and / or, The particle size D50 of the transparent bio-based polyamide resin composition powder is less than 50 micrometers; and / or, The water-soluble polymer is selected from one or more of nonionic water-soluble cellulose, nonionic water-soluble hydroxypropyl methylcellulose, and polyvinyl alcohol; and / or, The surfactant is selected from one or more of Fluorad 431, octadecylbenzyldimethylammonium chloride, and castor oil polyoxyethylene ether; and / or, The viscosity reducer is selected from one or more of 1,3-butanediol and ethylene glycol series; And / or, the method for preparing the slurry containing the transparent bio-based polyamide resin composition powder includes: taking materials according to the proportion of each component in the slurry, first mixing and stirring an appropriate amount of water, surfactant, and viscosity reducer to obtain a solution; dissolving the water-soluble polymer separately with water, and then adding it to the above solution and stirring; slowly adding the transparent bio-based polyamide resin composition powder in batches to the above solution and stirring to obtain the slurry. And / or, the viscosity of the mud is 0.1 to 100 cps.

16. The method for preparing the continuous fiber reinforced transparent bio-based polyamide composite material according to claim 15, characterized in that, The particle size D50 of the transparent bio-based polyamide resin composition powder is less than or equal to 5 micrometers; And / or, the viscosity of the mud is 2 to 30 cps.

17. The method for preparing the continuous fiber-reinforced transparent bio-based polyamide composite material according to claim 14, characterized in that, The fiber accounts for 50-70% of the mass percentage of the continuous fiber-reinforced transparent bio-based polyamide composite material. And / or, in step S2, before the fiber is pulled through the mud, the fiber also includes the following operation: the fiber is unwound from the yarn rack by a tension controller, passes through a yarn splitting frame, enters the yarn spreading system to fully spread each filament bundle, and is then pulled through the mud. And / or, the traction is performed using a traction device, and the traction speed is 3 to 12 m / min; And / or, the heating temperature is 290–310°C.

18. A molded article comprising the continuous fiber-reinforced transparent bio-based polyamide composite material according to any one of claims 1 to 13.

19. The application of a continuous fiber reinforced transparent bio-based polyamide composite material according to any one of claims 1 to 13 in the aerospace, military, automotive, sporting goods, building materials or electronic and electrical applications.

Images